JP2004168748A - Acenaphthylene derivative, polymer and antireflection film forming composition - Google Patents

Abstract

（式中、Ｒ¹ は水素原子または１価の有機基を示し、Ｒ² およびＲ³ は１価の原子または１価の有機基を示す。）
反射防止膜形成組成物は、該構造単位および／またはベンゼン環に基−ＣＨ₂ ＯＲ⁴(但し、Ｒ⁴ は水素原子または１価の有機基を示す。）を有するスチレン類あるいはビニルナフタレン類に対応する構造単位を有する重合体と溶剤を含有する。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an antireflection film-forming composition which has a high antireflection effect and does not cause intermixing, particularly a polymer useful for the antireflection film-forming composition, and particularly a raw material or an intermediate of the polymer. To provide acenaphthylene derivatives useful as
SOLUTION: The acenaphthylene derivative comprises acetoxymethylacenaphthylene and hydroxymethylacenaphthylene.
The polymer has a structural unit represented by the following formula (3).
Embedded image

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group, and R ² and R ³ represent a monovalent atom or a monovalent organic group.)
The composition for forming an anti-reflection film is preferably a styrene or vinyl naphthalene having a group —CH ₂ OR ⁴ (where R ⁴ represents a hydrogen atom or a monovalent organic group) on the structural unit and / or the benzene ring. It contains a polymer having a corresponding structural unit and a solvent.
[Selection diagram] None

Description

  The present invention is acetoxymethylacenaphthylene and hydroxymethylacenaphthylene, a polymer that can be produced from the acetoxymethylacenaphthylene or the hydroxymethylacenaphthylene, and containing the polymer, various radiation The present invention relates to a composition for forming an antireflection film suitable for fine processing in a lithography process to be used, particularly for production of highly integrated circuit elements.

It is well known to polymerize acenaphthylene to obtain polyacenaphthylene and to copolymerize acenaphthylene with styrene or maleic anhydride to obtain a copolymer.
Since such acenaphthylene (co) polymers have a unique structure and are highly reactive, not only the chemical modification by reaction with various reactive reagents has been studied, but also various physical properties such as luminescence behavior. Various materials and applications have been developed which are reported in detail, and which focus on properties such as low hygroscopicity, low birefringence, and low dielectric constant.
In the development of acenaphthylene (co) polymers that are highly reactive and can be expected to have various properties, it is a scientific and practical application to provide acenaphthylene derivatives having various functional groups that are useful as raw materials for the production thereof. This is extremely significant from a technical point of view, and an acenaphthylene derivative in which an aromatic ring is substituted with, for example, a hydroxyl group, an alkyl group, a halomethyl group, a halogen or the like has already been synthesized.
However, an acenaphthylene derivative in which an aromatic ring is substituted with an acetoxymethyl group or a hydroxymethyl group has not been reported so far.

  Further, in a method of manufacturing an integrated circuit device, a processing size in a lithography process is becoming finer in order to obtain a higher degree of integration. In this lithography process, a desired pattern is obtained by applying a resist composition solution onto a substrate, transferring a mask pattern by a reduction projection exposure apparatus (stepper), and developing with a suitable developing solution. However, substrates having high reflectivity such as aluminum, aluminum-silicon alloy, aluminum-silicon-copper alloy, polysilicon, and tungsten silicide used in this process do not have a resist pattern because exposed radiation is reflected on the substrate surface. There is a problem that halation occurs and a fine resist pattern cannot be accurately reproduced.

  In order to solve this problem, it has been proposed to provide an antireflection film having a property of absorbing radiation reflected from the substrate surface under a resist film to be formed on the substrate. As such an antireflection film, an inorganic film such as a titanium film, a titanium dioxide film, a titanium nitride film, a chromium oxide film, a carbon film, and an α-silicon film formed by a method such as vacuum deposition, CVD, and sputtering. Although known, these inorganic antireflection films have conductivity and cannot be used for the manufacture of integrated circuits, or special antireflection films such as vacuum deposition equipment, CVD equipment, and sputtering equipment are used for the formation of antireflection coatings. However, there are drawbacks such as the necessity of the device.

In order to solve the drawbacks of the inorganic antireflection film, an organic antireflection film comprising a polyamic acid (co) polymer or polysulfone (co) polymer and a dye has been proposed (for example, see Patent Document 1). ). This antireflection film has no conductivity, and the composition used for its formation is dissolved in a general solvent, so the special device as described above is not required. Can be easily applied to the substrate.
However, the antireflection film composed of a polyamic acid (co) polymer or polysulfone (co) polymer and a dye cannot sufficiently prevent halation or standing waves due to the limitation of the amount of the dye added, and also has a problem of resist coating. (This is referred to as intermixing), which causes a problem that the cross-sectional shape (pattern profile) of the resist pattern is deteriorated such as a poor defect or a footing.

On the other hand, it is known that when the polymer having an acenaphthylene skeleton is applied to an antireflection film, the above-described problems can be considerably solved (for example, see Patent Documents 2 and 3). The problem of intermixing has not been sufficiently solved in the prevention film.
Therefore, as a method of solving this problem, a method of crosslinking a polymer having an acenaphthylene skeleton with formaldehyde or the like can be considered. However, when such a method is used, the storage stability of the antireflection film-forming composition in a solution state is considered. Is disadvantageously reduced.
Therefore, development of an improved antireflection film capable of solving such problems in the prior art and a polymer particularly useful as a polymer component of the antireflection film has been desired.

JP-A-59-93448 JP 2000-143937 A JP 2001-40293 A

  An object of the present invention is to provide an antireflection film forming composition which can overcome the above-mentioned conventional problems, has a high antireflection effect, and does not cause intermixing, and can form a resist pattern having excellent resolution, pattern shape, and the like. In particular, it is an object of the present invention to provide a polymer useful as a component of the antireflection film-forming composition, and an acenaphthylene derivative particularly useful as a raw material or an intermediate of the polymer.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, using acenaphthene, which is easily available, as a starting material, a novel acenaphthylene derivative that can be easily synthesized through a process well-known as an organic synthesis reaction, A novel polymer having an aromatic ring in which a specific substituent is introduced, which is extremely useful as a raw material or an intermediate of a polymer that can effectively solve the above-mentioned problem in the antireflection film, and which can be produced from the acenaphthylene derivative. , Having a high absorbance to excimer lasers and the like, and having a higher refractive index compared to conventional antireflection films, and by using the polymer in the antireflection film forming composition, it is possible to obtain an excellent antireflection film. The present inventors have found out the present invention.

The present invention firstly
It consists of acetoxymethyl acenaphthylene represented by the following formula (1).

The present invention, secondly,
It consists of hydroxymethyl acenaphthylene represented by the following formula (2).

The present invention is, thirdly,
It has a structural unit represented by a structural unit represented by the following formula (3) (hereinafter referred to as “structural unit (3)”), and has a weight average molecular weight in terms of polystyrene of 500 measured by gel permeation chromatography (GPC). -10,000 polymers (hereinafter, referred to as "polymer (I)").

〔式（３）において、Ｒ¹ は水素原子または１価の有機基を示し、Ｒ² およびＲ³ は相互に独立に１価の原子または１価の有機基を示す。〕

[In the formula (3), R ¹ represents a hydrogen atom or a monovalent organic group, and R ² and R ³ independently represent a monovalent atom or a monovalent organic group. ]

Fourth, the present invention provides:
An anti-reflective coating forming composition comprising the polymer (I) and a solvent.

The present invention is, fifthly,
It contains a polymer having a structural unit represented by the following formula (4) (hereinafter, referred to as “structural unit (4)”) (hereinafter, referred to as “polymer (II)”) and a solvent. Anti-reflection film forming composition.

〔式（４）において、Ｒ⁴ は水素原子または１価の有機基を示し、Ｒ⁵ は１価の原子または１価の有機基を示し、ｎは０または１である。〕

[In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent atom or a monovalent organic group, and n is 0 or 1. ]

Sixth, the present invention provides
A polymer having a structural unit (3) and a structural unit (4) (hereinafter, referred to as “polymer (III)”), a structural unit (3) and a structural unit represented by the following formula (5) (hereinafter, referred to as “polymer (III)”) (Hereinafter, referred to as “polymer (IV)”), and a polymer having structural unit (4) and structural unit (5) (hereinafter, referred to as “polymer (IV)”). Polymer (V) "), and a composition for forming an antireflection film, characterized by containing a solvent.

〔式（５）において、Ｒ⁶ およびＲ⁷ は相互に独立に１価の原子または１価の有機基を示す。〕

[In the formula (5), R ⁶ and R ⁷ independently represent a monovalent atom or a monovalent organic group. ]

Hereinafter, the present invention will be described in detail.
Acetoxymethylacenaphthylene and hydroxymethylacenaphthylene The acetoxymethyl group in the formula (1) and the hydroxylmethyl group in the formula (2) are respectively bonded to any of the 3- to 5-positions of acenaphthylene.
Acetoxymethylacenaphthylene (hereinafter, referred to as “acetoxymethylacenaphthylene (1)”) represented by the formula (1) can be synthesized by, for example, the following first to fourth steps, Hydroxymethylacenaphthylene (hereinafter, referred to as “hydroxymethylacenaphthylene (2)”) represented by (2) can be synthesized, for example, by the following fifth step.

First step: As shown in the following formula (i), acenaphthene is formylated by a conventional method.

Second step: As shown in the following formula (ii), the formyl group of the formylacenaphthene obtained in the first step is reduced by a conventional method to obtain hydroxymethylacenaphthene.

Third step: As shown in the following formula (iii), the hydroxyl group of hydroxymethylacenaphthene obtained in the second step is acetylated by a conventional method to obtain acetoxymethylacenaphthene.

Fourth step: As shown in the following formula (iv), the acetoxymethyl acenaphthene obtained in the third step is dehydrogenated by a conventional method to obtain acetoxymethyl acenaphthylene (1).

Fifth step: As shown in the following formula (v), the acetoxy group of acetoxymethylacenaphthylene obtained in the fourth step is hydrolyzed by a conventional method to obtain hydroxymethylacenaphthylene (2).

  Acetoxymethyl acenaphthylene (1) can be used very suitably as a raw material or an intermediate for producing the polymer (I), and a raw material or an intermediate for producing the polymer (III) and the polymer (IV). It is also useful as a raw material, can be used very suitably as a raw material for synthesizing hydroxymethylacenaphthylene (2), and is also useful as a raw material or intermediate for synthesizing other related acenaphthylene derivatives.

  Hydroxymethylacenaphthylene (2) can be used very suitably as a raw material or an intermediate for producing the polymer (I), and a raw material or an intermediate for producing the polymer (III) and the polymer (IV). It is also useful as a raw material, and can be very suitably used as a raw material for synthesizing acetoxymethyl acenaphthylene (1), and is also useful as a raw material or intermediate for synthesizing other related acenaphthylene derivatives.

Polymer (I)
In the structural unit (3), as the monovalent organic group for R ¹ , a group having 1 to 10 carbon atoms is preferable. Examples of the preferable organic group include a phenyl group, an alkyl group, an alkenyl group, and an acyl group. And a group in which a phenyl group, an alkyl group or an alkenyl group is substituted with one or more of a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group, a sulfonic acid group and the like.

As the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group are more preferable. -Butyl group, sec-butyl group, t-butyl group and the like.
The alkenyl group is preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, more preferably a vinyl group, an allyl group, a methallyl group, a 1-butenyl group, a 2-butenyl group or the like. is there.
The acyl group is preferably an aliphatic or aromatic acyl group having 2 to 6 carbon atoms, more preferably an acetyl group, a propionyl group, a butyryl group, a benzoyl group and the like.

In the structural unit (3), examples of the monovalent atom of R ² and R ³ include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the monovalent organic group for R ² and R ³ include the same groups as those described above for the monovalent organic group for R ¹ .

In the structural unit (3), R ¹ is particularly preferably a hydrogen atom, a methyl group, an acetyl group, or the like.
R ² and R ³ are each preferably a hydrogen atom, a methyl group, a phenyl group, or the like.

The polymer (I) is, for example, mass polymerization, solution polymerization of acenaphthylenes corresponding to the structural unit (3) together with other copolymerizable unsaturated compounds, if necessary, by radical polymerization, anionic polymerization, or cationic polymerization. It can be produced by polymerizing in an appropriate polymerization form such as
Further, the polymer (I) having the structural unit (3) in which R ¹ is a hydrogen atom is prepared by hydrolyzing the acetoxy group of the polymer (I) having the structural unit (3) in which R ¹ is an acetyl group by an ordinary method. The polymer (I) having the structural unit (3) in which R ¹ is an acetyl group is a polymer (I) having the structural unit (3) in which R ¹ is a hydrogen atom. ) Can also be produced by acetylating the hydroxyl group in a conventional manner.

Acenaphthylenes corresponding to the structural unit (3) include, for example,
3-hydroxymethylacenaphthylene, 4-hydroxymethylacenaphthylene, 5-hydroxymethylacenaphthylene,
1-methyl-3-hydroxymethylacenaphthylene, 1-methyl-4-hydroxymethylacenaphthylene, 1-methyl-5-hydroxymethylacenaphthylene, 1-methyl-6-hydroxymethylacenaphthylene, 1- Methyl-7-hydroxymethylacenaphthylene, 1-methyl-8-hydroxymethylacenaphthylene, 1,2-dimethyl-3-hydroxymethylacenaphthylene, 1,2-dimethyl-4-hydroxymethylacenaphthylene, 1,2-dimethyl-5-hydroxymethylacenaphthylene, 1-phenyl-3-hydroxymethylacenaphthylene, 1-phenyl-4-hydroxymethylacenaphthylene, 1-phenyl-5-hydroxymethylacenaphthylene, 1-phenyl-6-hydroxymethylacenaphthylene, 1-phenyl-7 Hydroxymethylacenaphthylene, 1-phenyl-8-hydroxymethylacenaphthylene, 1,2-diphenyl-3-hydroxymethylacenaphthylene, 1,2-diphenyl-4-hydroxymethylacenaphthylene, 1,2- Hydroxymethylacenaphthylenes such as diphenyl-5-hydroxymethylacenaphthylene;

3-acetoxymethylacenaphthylene, 4-acetoxymethylacenaphthylene, 5-acetoxymethylacenaphthylene,
1-methyl-3-acetoxymethylacenaphthylene, 1-methyl-4-acetoxymethylacenaphthylene, 1-methyl-5-acetoxymethylacenaphthylene, 1-methyl-6-acetoxymethylacenaphthylene, Methyl-7-acetoxymethylacenaphthylene, 1-methyl-8-acetoxymethylacenaphthylene, 1,2-dimethyl-3-acetoxymethylacenaphthylene, 1,2-dimethyl-4-acetoxymethylacenaphthylene, 1,2-dimethyl-5-acetoxymethylacenaphthylene, 1-phenyl-3-acetoxymethylacenaphthylene, 1-phenyl-4-acetoxymethylacenaphthylene, 1-phenyl-5-acetoxymethylacenaphthylene, 1-phenyl-6-acetoxymethylacenaphthylene, 1-phenyl-7 Acetoxymethylacenaphthylene, 1-phenyl-8-acetoxymethylacenaphthylene, 1,2-diphenyl-3-acetoxymethylacenaphthylene, 1,2-diphenyl-4-acetoxymethylacenaphthylene, 1,2- Acetoxymethylacenaphthylenes such as diphenyl-5-acetoxymethylacenaphthylene;

3-methoxymethylacenaphthylene, 4-methoxymethylacenaphthylene, 5-methoxymethylacenaphthylene,
1-methyl-3-methoxymethylacenaphthylene, 1-methyl-4-methoxymethylacenaphthylene, 1-methyl-5-methoxymethylacenaphthylene, 1-methyl-6-methoxymethylacenaphthylene, 1- Methyl-7-methoxymethylacenaphthylene, 1-methyl-8-methoxymethylacenaphthylene, 1,2-dimethyl-3-methoxymethylacenaphthylene, 1,2-dimethyl-4-methoxymethylacenaphthylene, 1,2-dimethyl-5-methoxymethylacenaphthylene, 1-phenyl-3-methoxymethylacenaphthylene, 1-phenyl-4-methoxymethylacenaphthylene, 1-phenyl-5-methoxymethylacenaphthylene, 1-phenyl-6-methoxymethylacenaphthylene, 1-phenyl-7-methoxymethylacenaphthyl 1-phenyl-8-methoxymethylacenaphthylene, 1,2-diphenyl-3-methoxymethylacenaphthylene, 1,2-diphenyl-4-methoxymethylacenaphthylene, 1,2-diphenyl-5- Methoxymethyl acenaphthylenes such as methoxymethyl acenaphthylene,

3-phenoxymethylacenaphthylene, 4-phenoxymethylacenaphthylene, 5-phenoxymethylacenaphthylene, 3-vinyloxymethylacenaphthylene, 4-vinyloxymethylacenaphthylene, 5-vinyloxymethylacenaphthylene And the like.

Among these acenaphthylenes, in particular, 3-hydroxymethylacenaphthylene, 4-hydroxymethylacenaphthylene, 5-hydroxymethylacenaphthylene, 3-acetoxymethylacenaphthylene, 4-acetoxymethylacenaphthylene, -Acetoxymethylacenaphthylene, 3-methoxymethylacenaphthylene, 4-methoxymethylacenaphthylene, 5-methoxymethylacenaphthylene and the like are preferred.
The acenaphthylenes can be used alone or in combination of two or more.

As the other copolymerizable unsaturated compound in the polymer (I), an aromatic vinyl compound corresponding to the structural unit (4) described later and acenaphthylene corresponding to the structural unit (5) described later are preferable.
Further, as other copolymerizable unsaturated compounds, for example,
Other aromatic vinyl compounds such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, and 9-vinylcarbazole ;
Vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl caproate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) Unsaturated carboxylic acid ester compounds such as acrylate and glycidyl (meth) acrylate;

Unsaturated group-containing unsaturated carboxylic acid ester compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, vinyl (meth) acrylate, and dimethyl vinyl (meth) acryloyloxymethylsilane;
Halogen-containing vinyl compounds such as 2-chloroethyl vinyl ether, vinyl chloroacetate and allyl chloroacetate;
Hydroxyl-containing vinyl compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and (meth) allyl alcohol;
Amide group-containing vinyl compounds such as (meth) acrylamide and crotonic acid amide; mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] maleate, mono [2 -(Meth) acryloyloxyethyl] and the like.
The other copolymerizable unsaturated compounds can be used alone or in combination of two or more.

The content of structural units derived from other copolymerizable unsaturated compounds in the polymer (I) is preferably at most 80 mol%, more preferably at most 60 mol%, particularly preferably at most 40 mol%, based on all structural units. Mol% or less.
The weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of the polymer (I) measured by gel permeation chromatography is from 500 to 10,000, preferably from 1,000 to 5,000.

  The polymer (I) has a property of causing a cross-linking reaction between molecular chains by heating or exposure, and is particularly useful for an antireflection film-forming composition described below, or alone or in other curable compositions. It can be used as a paint, an adhesive, an insulating material, a molded product, etc. by being mixed with a resin or a curable rubber.

Antireflection film forming composition The antireflection film forming composition of the present invention contains (A) polymer (I) and a solvent, (B) polymer (II) and a solvent, or (C) ) It contains at least one selected from the group consisting of polymer (III), polymer (IV) and polymer (V), and a solvent.
Hereinafter, the polymers (II) to (V) and the solvent, which are constituent components of each antireflection film-forming composition, will be sequentially described.

-Polymer (II)-
In the structural unit (4), examples of the monovalent organic group for R ⁴ include the same groups as those exemplified for the monovalent organic group for R ¹ in the structural unit (3). the monovalent atoms and monovalent organic groups of ^5, for example, include the same as those exemplified for each monovalent atoms and monovalent organic groups of R ² and R ³ in the structural unit (3) be able to.

In the structural unit (4), R ⁴ is particularly preferably a hydrogen atom, a methyl group, or the like.
R ⁵ is particularly preferably a hydrogen atom, a methyl group or the like.

The polymer (II) is obtained by subjecting an aromatic vinyl compound corresponding to the structural unit (4), together with another copolymerizable unsaturated compound, if necessary, to radical polymerization, anionic polymerization, cationic polymerization, or the like, to form a bulk polymerization, a solution, or the like. It can be produced by polymerizing in an appropriate polymerization form such as polymerization.
The polymer (II) having the structural unit (4) in which R ⁴ is a hydrogen atom is prepared by hydrolyzing the acetoxy group of the polymer (II) having the structural unit (4) in which R ⁴ is an acetyl group by a conventional method. The polymer (II) having the structural unit (4) in which R ⁴ is an acetyl group can be produced by decomposing the polymer (II) having the structural unit (4) in which R ⁴ is a hydrogen atom. ) Can also be produced by acetylating the hydroxyl group in a conventional manner.

Preferred aromatic vinyl compounds corresponding to the structural unit (4) include, for example, 2-hydroxymethylstyrene, 3-hydroxymethylstyrene, 4-hydroxymethylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxy Hydroxymethylstyrene compounds such as methyl-α-methylstyrene and 4-hydroxymethyl-α-methylstyrene;
Methoxy such as 2-methoxymethylstyrene, 3-methoxymethylstyrene, 4-methoxymethylstyrene, 2-methoxymethyl-α-methylstyrene, 3-methoxymethyl-α-methylstyrene, 4-methoxymethyl-α-methylstyrene Methylstyrene-based compounds;
4-phenoxymethylstyrene, 4-phenoxymethyl-α-methylstyrene, 4-vinyloxymethylstyrene, 4-vinyloxymethyl-α-methylstyrene, 4-acetoxymethylstyrene, 4-acetoxymethyl-α-methylstyrene, etc. Other styrenic compounds;

4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenyl Naphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, 1-hydroxymethyl-2-vinylnaphthalene, 1-hydroxymethyl-3-vinylnaphthalene, 1-hydroxymethyl-4-vinylnaphthalene, 1-hydroxymethyl-5- Vinyl naphthalene, 1-hydroxymethyl-6-vinylnaphthalene, 1-hydroxymethyl-7-vinylnaphthalene, 1-hydroxymethyl-8-vinylnaphthalene, 2-hydroxymethyl-3-vinylnaphthalene, 2-hydroxymethyl-4- Sulfonyl naphthalene, 2-hydroxymethyl-5-vinylnaphthalene, 2-hydroxymethyl-6-vinylnaphthalene, 2-hydroxymethyl-7-vinylnaphthalene hydroxymethyl - vinylnaphthalene compounds;

4-methoxymethyl-1-vinylnaphthalene, 7-methoxymethyl-1-vinylnaphthalene, 8-methoxymethyl-1-vinylnaphthalene, 4-methoxymethyl-1-isopropenylnaphthalene, 7-methoxymethyl-1-isopropenyl Methoxymethyl-1-vinylnaphthalene-based compounds such as naphthalene and 8-methoxymethyl-1-isopropenylnaphthalene;
4-phenoxymethyl-1-vinylnaphthalene, 4-vinyloxymethyl-1-vinylnaphthalene, 4-acetoxymethyl-1-vinylnaphthalene, 4-phenoxymethyl-1-isopropenylnaphthalene, 4-vinyloxymethyl-1- Other vinyl naphthalene compounds such as isopropenyl naphthalene and 4-acetoxymethyl-1-isopropenyl naphthalene can be exemplified.

Among these aromatic vinyl compounds, 4-hydroxymethylstyrene, 4-methoxymethylstyrene, 2-hydroxymethyl-6-vinylnaphthalene and the like are particularly preferable.
The aromatic vinyl compounds can be used alone or in combination of two or more.

Further, as other copolymerizable unsaturated compounds in the polymer (II), for example, the same compounds as those exemplified for the other copolymerizable unsaturated compounds in the polymer (I) can be mentioned.
Of these other copolymerizable unsaturated compounds, styrene is particularly preferred.
The other copolymerizable unsaturated compounds can be used alone or in combination of two or more.

The content of structural units derived from other copolymerizable unsaturated compounds in the polymer (II) is preferably at most 80 mol%, more preferably at most 60 mol%, particularly preferably at most 40 mol%, based on all structural units. Mol% or less.
The Mw of the polymer (II) is appropriately selected according to the desired properties of the antireflection film, and is usually from 500 to 10,000, preferably from 1,000 to 5,000.

-Polymers (III) to (V)-
The structural unit (3) in the polymer (III) and the polymer (IV) is the same as the structural unit (3) in the polymer (I), and the structural unit (3) in the polymer (IV) and the polymer (V) The structural unit (4) is the same as the structural unit (4) in the polymer (II).

In the structural unit (5), examples of the monovalent atom or monovalent organic group of R ⁶ and R ⁷ include, for example, the monovalent atom or monovalent organic group of R ² and R ³ in the structural unit (3). The same as those exemplified for the group can be exemplified.

In the structural unit (5), each of R ⁶ and R ⁷ is particularly preferably a hydrogen atom, a methyl group, or the like.

The polymer (III) is obtained by polymerizing acenaphthylenes corresponding to the structural unit (3) and an aromatic vinyl compound corresponding to the structural unit (4), optionally together with another copolymerizable unsaturated compound. The polymer (IV) is obtained by combining acenaphthylenes corresponding to the structural unit (3) and acenaphthylenes corresponding to the structural unit (5) together with another copolymerizable unsaturated compound in some cases. The polymer (V) can be produced by polymerizing an aromatic vinyl compound corresponding to the structural unit (4) and an acenaphthylene corresponding to the structural unit (5). And a copolymerizable unsaturated compound of the formula (1).
Each polymerization for producing the polymers (III) to (V) can be carried out in an appropriate polymerization form such as bulk polymerization, solution polymerization, or the like by, for example, radical polymerization, anionic polymerization, or cationic polymerization.

Further, a polymer (III) having a structural unit (3) in which R ¹ is a hydrogen atom or a structural unit (4) in which R ⁴ is a hydrogen atom, and a polymer having a structural unit (3) in which R ¹ is a hydrogen atom. The copolymer (IV) and the polymer (V) having the structural unit (4) wherein R ⁴ is a hydrogen atom can be prepared by a conventional method using the acetoxymethyl group in the polymers (III) to (V) each having an acetoxymethyl group. And a polymer (III) having a structural unit (3) in which R ¹ is an acetyl group or a structural unit (4) in which R ⁴ is an acetyl group, wherein R ¹ is acetyl. The polymer (IV) having a structural unit (3) as a group and the polymer (V) having a structural unit (4) wherein R ⁴ is an acetyl group are polymers (III) to ( Each hydroxyl group in V) is acetylated by a conventional method. It can also be manufactured by

In the polymer (III) and the polymer (IV), the acenaphthylenes corresponding to the structural unit (3) include, for example, the same as the compounds exemplified for the acenaphthylenes corresponding to the structural unit (3) in the polymer (I). Can be mentioned. Among these acenaphthylenes, in particular, 3-hydroxymethylacenaphthylene, 4-hydroxymethylacenaphthylene, 5-hydroxymethylacenaphthylene, 3-methoxymethylacenaphthylene, 4-methoxymethylacenaphthylene, -Methoxymethylacenaphthylene and the like are preferred.
The acenaphthylenes can be used alone or in combination of two or more.

In the polymer (III) and the polymer (V), examples of the aromatic vinyl compound corresponding to the structural unit (4) include, for example, an aromatic vinyl compound corresponding to the structural unit (4) in the polymer (II). The same compounds as the system compounds can be mentioned.
Among these aromatic vinyl compounds, 4-hydroxymethylstyrene, 4-methoxymethylstyrene and the like are particularly preferable.
The aromatic vinyl compounds can be used alone or in combination of two or more.

In the polymer (IV) and the polymer (V), preferred acenaphthylenes corresponding to the structural unit (5) include, for example, acenaphthylene, 1-methylacenaphthylene, 1,2-dimethylacenaphthylene, -Phenylacenaphthylene, 1,2-diphenylacenaphthylene, 1-methyl-2-phenylacenaphthylene and the like.
Of these acenaphthylenes, acenaphthylene is particularly preferred.
The acenaphthylenes can be used alone or in combination of two or more.
Examples of the other copolymerizable unsaturated compounds in the polymers (III) to (V) include, for example, those similar to the other copolymerizable unsaturated compounds in the polymer (I). it can.
These other copolymerizable unsaturated compounds can be used alone or in combination of two or more.

  In the polymer (III), the content of the structural unit (3) is preferably from 5 to 80 mol%, more preferably from 10 to 60 mol%, particularly preferably from 10 to 40 mol%, based on all structural units. The content of the structural unit (4) is preferably from 5 to 80 mol%, more preferably from 5 to 60 mol%, particularly preferably from 5 to 40 mol%, based on all structural units. The content of the structural unit derived from the polymerizable unsaturated compound is preferably 50 mol% or less, more preferably 30 mol% or less, based on all structural units.

  In the polymer (IV), the content of the structural unit (3) is preferably from 5 to 80 mol%, more preferably from 10 to 60 mol%, particularly preferably from 10 to 40 mol%, based on all structural units. The content of the structural unit (5) is preferably from 5 to 95 mol%, more preferably from 10 to 90 mol%, particularly preferably from 20 to 90 mol%, based on all structural units. The content of the structural unit derived from the polymerizable unsaturated compound is preferably 50 mol% or less, more preferably 30 mol% or less, based on all structural units.

  In the polymer (V), the content of the structural unit (4) is preferably from 5 to 80 mol%, more preferably from 10 to 60 mol%, particularly preferably from 15 to 60 mol%, based on all structural units. The content of the structural unit (5) is preferably from 5 to 95 mol%, more preferably from 10 to 90 mol%, particularly preferably from 20 to 80 mol%, based on all structural units. The content of the structural unit derived from the polymerizable unsaturated compound is preferably 50 mol% or less, more preferably 30 mol% or less, based on all structural units.

  The Mw of the polymer (III), the polymer (IV) and the polymer (V) is appropriately selected according to the desired properties of the antireflection film, but is usually 500 to 10,000, preferably 500 to 5 , 000.

-Solvent-
The solvent used in each antireflection film-forming composition of the present invention is not particularly limited as long as it can dissolve each of the polymers and the additive components described below.
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate and ethylene glycol mono-n-butyl ether acetate;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, and diethylene glycol di-n-butyl ether;
Triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, and propylene glycol di-n-butyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;

Lactic esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate, i-butyl lactate;
Methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-acetic acid Propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-propionate Aliphatic carboxylic acid esters such as -butyl, i-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, i-butyl butyrate;

Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, Other esters such as -methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Lactones such as γ-butyrolactone are appropriately selected and used.

Among these solvents, ethylene glycol monoethyl ether acetate, ethyl lactate, n-butyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone and the like are preferable.
The solvents may be used alone or in combination of two or more.

  The amount of the solvent to be used is such that the solid concentration of the obtained composition is usually 0.01 to 70% by weight, preferably 0.05 to 60% by weight, and more preferably 0.1 to 50% by weight. is there.

-Additive-
The antireflection film-forming composition of the present invention, as long as the desired effect of the present invention is not impaired, if necessary, an acid generator, a crosslinking agent, a binder resin, a radiation absorber, various surfactants such as a surfactant. An additive can be blended, and it is particularly preferable to blend an acid generator and / or a crosslinking agent.

The acid generator is a component that generates an acid upon exposure or heating.
Examples of the acid generator that generates an acid upon exposure (hereinafter, referred to as “photoacid generator”) include, for example,
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalene sulfonate, diphenyliodonium hexafluoroantimonate,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis ( 4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate,
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium hexafluoroantimonate,
4-hydroxyphenyl-phenyl-methylsulfonium p-toluenesulfonate, 4-hydroxyphenyl-benzyl-methylsulfonium p-toluenesulfonate,

Cyclohexylmethyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldicyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate,
1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1- Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 4-hydroxy- 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4 Hydroxy-1-naphthyl diethyl sulfonium trifluoromethane sulfonate,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene-1-) Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane Sulfonate,
1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n -Propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,

1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1 -[4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate,
Onium salt-based photoacid generators such as 1- (4-benzyloxy) tetrahydrothiophenium trifluoromethanesulfonate and 1- (naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate;

Halogen-containing compound-based photoacid generators such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine;
1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone or Diazoketone compound-based photoacid generators such as 1,2-naphthoquinonediazide-5-sulfonic acid ester;
Sulfone compound-based photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane;
Benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-di Examples thereof include sulfonic acid compound-based photoacid generators such as carbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these photoacid generators, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalene sulfonate, Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis ( 4-tert-butylphenyl) iodonium 10-camphorsulfonate, bis (4-tert-butylphenyl) Etc. iodonium naphthalene sulfonate is preferred.
The photoacid generators can be used alone or in combination of two or more.

Examples of the acid generator that generates an acid by heating (hereinafter, referred to as “thermal acid generator”) include, for example, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl Tosylate, alkyl sulfonates and the like can be mentioned.
These thermal acid generators can be used alone or in combination of two or more.
Further, a photoacid generator and a thermal acid generator can be used in combination as the acid generator.

  The amount of the acid generator is usually 5,000 parts by weight or less, preferably 0.1 to 1,000 parts by weight, more preferably 0.1 to 1,000 parts by weight, per 100 parts by weight of the solid content of the antireflection film-forming composition. 100 parts by weight. The composition for forming an antireflection film of the present invention contains a photoacid generator and / or a thermal acid generator, so that a cross-linking reaction is effectively generated between molecular chains of each polymer at a relatively low temperature including room temperature. It becomes possible.

Further, the crosslinking agent is a component having an effect of preventing intermixing between the obtained antireflection film and a resist film formed thereon, and further, preventing cracking of the antireflection film.
As such a crosslinking agent, polynuclear phenols and various commercially available curing agents can be used.
Examples of the polynuclear phenols include dinuclear phenols such as 4,4'-biphenyldiol, 4,4'-methylenebisphenol, 4,4'-ethylidenebisphenol, and bisphenol A; 4,4 ', 4'' Trinuclear phenols such as -methylidene trisphenol, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol; polyphenols such as novolak Can be mentioned.
Among these polynuclear phenols, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, novolak and the like are preferable.
The polynuclear phenols can be used alone or in combination of two or more.

Examples of the curing agent include 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, and 4,4 ′. -Diisocyanates such as diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1,4-cyclohexane diisocyanate, and Epicoat 812, 815, 826, 828, 834, and 836 under the following trade names. , 871, 1001, 1004, 1007, 1009, 1031 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite 6600, 6700, 6800, 502, 6071, 6084, 6097, 6099 (all manufactured by Ciba-Geigy), DER331, 332, 333, 66 Epoxy compounds such as 1, 644, and 667 (both manufactured by Dow Chemical Company); Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, and 712; Melamine-based curing agents such as 701, 272, 202, Mycoat 506, and 508 (all manufactured by Mitsui Cyanamid Co., Ltd.); Cymel 1123, 1123-10, 1128, Mycoat 102, and 105; Benzoguanamine-based curing agents such as 106 and 130 (manufactured by Mitsui Cyanamid Co., Ltd.); Cymel 1170 and 1172 (manufactured by Mitsui Cyanamid Co., Ltd.), Nikarac N-2702 (manufactured by Sanwa Chemical Co., Ltd.) ) And the like.
Among these curing agents, melamine-based curing agents, glycoluril-based curing agents, and the like are preferable. The curing agents may be used alone or in combination of two or more.
In addition, a polynuclear phenol and a curing agent can be used in combination as a crosslinking agent.

  The amount of the crosslinking agent is usually 5,000 parts by weight or less, preferably 1,000 parts by weight or less, per 100 parts by weight of the solid content of the antireflection film-forming composition.

Further, as the binder resin, various thermoplastic resins and thermosetting resins can be used.
As the thermoplastic resin, for example,
Polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene, poly-1-dodecene, poly-1- Α-olefin polymers such as tetradecene, poly-1-hexadecene, poly-1-octadecene, and polyvinylcycloalkane; poly-1,4-pentadiene, poly-1,4-hexadiene, poly-1,5-hexadiene Non-conjugated diene polymers such as
α, β-unsaturated aldehyde polymers; α, β-unsaturated ketone polymers such as poly (methyl vinyl ketone), poly (aromatic vinyl ketone), and poly (cyclic vinyl ketone); (meth) acrylic acid Polymers of α, β-unsaturated carboxylic acids or derivatives thereof, such as, α-chloroacrylic acid, (meth) acrylate, (meth) acrylate, (meth) acrylic halide; poly (meth) Α, β-unsaturated carboxylic acid anhydride polymers such as copolymers of acrylic acid anhydride and maleic anhydride; polymers of unsaturated polybasic carboxylic acid esters such as methylenemalonic acid diester and itaconic acid diester Kind;

Polymers of diolefin carboxylic acid esters such as sorbic acid ester and muconic acid ester; Polymers of α, β-unsaturated carboxylic acid thioester such as (meth) acrylic acid thioester and α-chloroacrylic acid thioester; ) Polymers of (meth) acrylonitrile or derivatives thereof such as acrylonitrile and α-chloroacrylonitrile; Polymers of (meth) acrylamide or derivatives thereof such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; styryl Polymers of metal compounds; Polymers of vinyloxy metal compounds;
Polyimines; polyethers such as polyphenylene oxide, poly-1,3-dioxolane, polyoxirane, polytetrahydrofuran, polytetrahydropyran; polysulfides; polysulfonamides; polypeptides; nylon 66, nylon 1 to nylon 12, and the like. Polyamides; Polyesters such as aliphatic polyesters, aromatic polyesters, alicyclic polyesters, and polycarbonates; Polyureas; Polysulfones; Polyazines; Polyamines; Polyaromatic Ketones; Polyimides; Polybenzimidazoles Polybenzoxazoles; polybenzothiazoles; polyaminotriazoles; polyoxadiazoles; polypyrazoles; polytetrazoles; polyquinoxalines; polytriazines; Down like; quinoline compounds; mention may be made of a poly-Anne tiger gelsolin, and the like.

Further, the thermosetting resin is a component having an effect of preventing intermixing between the obtained antireflection film and a resist film formed thereon, which is cured by heating and becomes insoluble in a solvent, It can be preferably used as a binder resin.
Such thermosetting resins include, for example, thermosetting acrylic resins, phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy resins, alkyd resins And the like.
Among these thermosetting resins, urea resins, melamine resins, aromatic hydrocarbon resins and the like are preferable.

The binder resins may be used alone or in combination of two or more.
The compounding amount of the binder resin is usually 20 parts by weight or less, preferably 10 parts by weight or less, per 100 parts by weight of the polymer of each antireflection film-forming composition.

Examples of the radiation absorber include dyes such as oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, and hydroxyazo dyes; bixin derivatives, norbixin, stilbene, Fluorescent whitening agents such as 4,4'-diaminostilbene derivatives, coumarin derivatives, and pyrazoline derivatives; hydroxyazo dyes, tinuvin 234 (trade name, manufactured by Ciba Geigy), tinuvin 1130 (trade name, manufactured by Ciba Geigy), and the like. UV absorbers; and aromatic compounds such as anthracene derivatives and anthraquinone derivatives.
These radiation absorbers can be used alone or in combination of two or more.
The content of the radiation absorber is usually 100 parts by weight or less, preferably 50 parts by weight or less, per 100 parts by weight of the solid content of the antireflection film-forming composition.

Further, the surfactant is a component having an action of improving applicability, striation, wettability, developability, and the like.
Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, and polyethylene. Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. No. 75, the same No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), F-Top EF101, EF204, EF303, and EF352 (manufactured by Tochem Products), Megafax F171, F172, and F173 (managed by Dainippon) Ink Chemical Industry Co., Ltd.), Florad FC430, FC431, FC135, FC93 (all manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105 and SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.
These surfactants can be used alone or in combination of two or more.
The amount of the surfactant is usually 15 parts by weight or less, preferably 10 parts by weight or less, per 100 parts by weight of the solid content of the antireflection film-forming composition.
Furthermore, examples of the additives other than those described above include a storage stabilizer, an antifoaming agent, and an adhesion aid.

Method of forming anti-reflective film The method of forming an anti-reflective film from each of the anti-reflective film forming compositions of the present invention (hereinafter, simply referred to as "composition") generally includes, for example, 1) coating the composition on a substrate Forming an anti-reflection film by curing the obtained coating film; 2) applying a resist composition solution on the anti-reflection film and pre-baking the obtained coating film to form a resist coating 3) selectively exposing the resist film via a photomask, 4) developing the exposed resist film, and 5) etching the antireflection film.

In step 1), for example, a silicon wafer, a wafer coated with aluminum, or the like can be used as the substrate. The application of the composition can be performed by an appropriate method such as spin coating, casting coating, roll coating and the like.
Thereafter, the coating film is cured by exposure and / or heating. The radiation to be exposed is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular beam, ion beam and the like according to the type of photoacid generator used. When the composition contains a photoacid generator and is exposed to light, the coating film can be effectively cured even at room temperature. The heating temperature is usually about 90 to 350 ° C., preferably about 200 to 300 ° C. When the composition contains a thermal acid generator, for example, the coating can be effectively formed at about 90 to 150 ° C. It is possible to cure.
The thickness of the antireflection film formed in the step 1) is usually 0.1 to 5 μm.

  Next, in step 2), a resist composition solution is applied on the antireflection film so that the obtained resist film has a predetermined thickness, and then prebaked, and the solvent in the coating film is volatilized, thereby forming a resist. Form a coating. The prebaking temperature at this time is appropriately adjusted depending on the type of the resist composition to be used and the like, but is usually about 30 to 200 ° C, preferably 50 to 150 ° C.

  As the resist composition, for example, a positive or negative type chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, an alkali-soluble resin A negative resist composition comprising a cross-linking agent can be exemplified.

  The resist composition solution used when forming the resist film on the antireflection film has a solid content concentration of usually about 5 to 50% by weight, and is generally filtered, for example, with a filter having a pore size of about 0.2 μm. To provide a resist film. In this step, a commercially available resist composition solution can be used as it is.

Next, in the step 3), the radiation used for the exposure includes visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, and molecule, depending on the type of the photoacid generator used in the resist composition. Although it is appropriately selected from a line, an ion beam, etc., it is preferably a deep ultraviolet ray, and in particular, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (wavelength 157 nm), a Kr ₂ excimer laser ( Wavelength 147 nm), ArKr excimer laser (wavelength 134 nm), extreme ultraviolet (wavelength 13 nm or the like) and the like are preferable.

  Next, in step 4), the resist film after exposure is developed, washed, and dried to form a predetermined resist pattern. In this step, post-baking can be performed after exposure and before development in order to improve resolution, pattern profile, developability, and the like.

  The developer used in this step is appropriately selected depending on the type of the resist composition used, but the development in the case of a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin is performed. Examples of the liquid include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, and dimethylethanol. Amine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. 0] -5-none Alkaline aqueous solution etc. may be mentioned. In addition, a suitable amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant can be added to these alkaline aqueous solutions.

  Next, in the step 5), by using the obtained resist pattern as a mask and performing dry etching of the antireflection film using gas plasma such as oxygen plasma, a resist pattern for processing a predetermined substrate is obtained.

The acetoxymethyl acenaphthylene (1) and the hydroxymethyl acenaphthylene (2) of the present invention can be used particularly suitably as raw materials or intermediates for producing the polymer (I).
The polymer (I) of the present invention can be particularly suitably used as a polymer component in each antireflection film-forming composition of the present invention.
Since the antireflection film formed using each antireflection film forming composition of the present invention has a high antireflection effect and does not cause intermixing with the resist film, various positive and negative resist compositions are used. And a resist pattern excellent in resolution, pattern shape, and the like can be provided. Therefore, each antireflection film forming composition of the present invention greatly contributes to the production of a highly integrated circuit.

Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these embodiments. In the following, “parts” and “%” are based on weight unless otherwise specified.
Example 1 (Synthesis of acenaphthylene derivative)
-First step-
Under a dry atmosphere, 150 g of tin chloride was added dropwise at −5 ° C. to a solution of 70 g of dichloromethyl methyl ether in 300 g of dichloroethane, and then a solution of 77 g of acenaphthene in 300 g of dichloroethane was added dropwise. Then, after stirring the reaction solution at room temperature for 2 hours, a 5% calcium chloride aqueous solution was gradually added dropwise. Thereafter, the organic phase was washed until the aqueous phase became neutral. Then, the organic layer was separated, and the solvent was distilled off to obtain 90.5 g of a pale yellow solid compound.
This compound had the following ¹ H-NMR spectrum (δ) (solvent: deuterated chloroform; the same applies hereinafter) and infrared absorption spectrum (IR), and was identified as formylacenaphthene.
δ (unit ppm): 3.4 (CH ₂ group);
7.3 to 8.8, 10.5 (above, CHO group).
IR (unit cm ^-1 ): 1677 (C = O group).

-Second step-
To a solution of 73 g of formylacenaphthene obtained in the first step in a mixed solvent of tetrahydrofuran / ethanol (550 g of tetrahydrofuran, 110 g of ethanol) was added 7.6 g of sodium borohydride, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was concentrated, water was added, and the precipitated compound was separated by filtration and dried under reduced pressure to obtain 71 g of a white solid compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as hydroxymethylacenaphthene.
δ (unit ppm): 3.3 (CH ₂ group);
4.8 to 4.9 (CH ₂ -O group);
5.2 to 5.3 (OH group);
7.2 to 7.8 (hydrogen atom of aromatic ring).
IR (unit cm ^-1 ): 3372, 3297 (above, OH group).

-Third step-
In a solution prepared by dissolving 55 g of hydroxymethylacenaphthene obtained in the second step in 1,200 g of dioxane, 26 g of acetyl chloride and 36 g of triethylamine were added dropwise in this order while maintaining the liquid temperature at 50 ° C. or lower, and then at 90 ° C. Stir for 3 hours. Thereafter, the insoluble matter was removed by filtration, the organic phase was concentrated, and the solvent was replaced with toluene. Thereafter, this toluene solution was washed with water until the aqueous phase became neutral, and then the solvent was distilled off to obtain 65 g of a yellow solid compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as acetoxymethylacenaphthene.
δ (unit ppm): 2.1 (CH ₃ group);
3.3 to 3.4 (CH ₂ group);
5.5 (CH ₂ —O group);
7.2 to 7.5 (hydrogen atom of aromatic ring).
IR (unit: cm ^-1 ): 1725 (C = O group).

-Fourth step-
After adding 60 g of dichlorodicyanobenzoquinone to a solution of 45 g of acetoxymethylacenaphthene obtained in the third step dissolved in 450 g of dioxane, the mixture was stirred at 95 ° C. for 7 hours. Thereafter, the reaction solution was separated by filtration, and the solvent was distilled off to obtain 54 g of acetoxymethylacenaphthylene as a brown solid.

-Fifth process-
110 g of a 10% aqueous NaOH solution was added dropwise to a solution of 44 g of acetoxymethylacenaphthylene in 300 g of methanol, followed by stirring at 60 ° C. for 2 hours. Thereafter, methanol was distilled off from the reaction solution, and the solvent was replaced with 350 g of methyl ethyl ketone. Thereafter, the methyl ethyl ketone solution was washed with water until the aqueous phase became neutral, and then the solvent was distilled off to obtain a yellow solid. Thereafter, the yellow solid was recrystallized and purified to obtain 10 g of a compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as hydroxymethylacenaphthylene.
δ (unit ppm): 5.1 (CH ₂ —O group),
5.4 (OH group),
7.2 (HC = CH group),
7.6 to 8.2 (hydrogen atom of aromatic ring).
IR (unit cm ^-1 ): 3423 (OH group).

Synthesis Example 1 (Synthesis of 2-hydroxymethyl-6-vinylnaphthalene)
Under a nitrogen atmosphere, 98 g of methyl 6-bromo-2-naphthalenecarboxylate was dissolved in 2 liters of 1,2-dimethoxyethane, and 44 g of tetrakis (triphenylphosphine) palladium was added, followed by stirring at room temperature for 30 minutes. Thereafter, 52 g of potassium carbonate, 1 liter of water and 91 g of 2,4,6-trivinylcyclotriboroxane / pyridine complex were added, and the mixture was stirred under heating and reflux for 24 hours. Thereafter, the reaction solution was returned to room temperature and passed through an activated alumina layer to obtain 77 g of methyl 2-vinyl-6-naphthalenecarboxylate.
Then, to a solution prepared by dissolving 30 g of methyl 2-vinyl-6-naphthalenecarboxylate in 500 ml of tetrahydrofuran was added 400 ml of a 1 mol / l di-i-butylaluminum hydride solution in tetrahydrofuran at −78 ° C. Stir for 1 hour. After completion of the reaction was confirmed by thin-layer chromatography, methanol and water were added and mixed, and the organic layer was extracted with ethyl acetate. Thereafter, the organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. Thereafter, the concentrate was purified by silica gel chromatography to obtain 18.5 g of a compound.
The compound had the following ¹ H-NMR spectrum (δ) and was identified as 2-hydroxymethyl-6-vinylnaphthalene.
δ (unit ppm): 4.9 (CH ₂ —O group),
5.3, 5.9, 6.9 (vinyl group),
7.6 to 7.8 (hydrogen atom of aromatic ring).

  In the following Preparation Example 1 and Examples 2 to 4, Mw of the obtained resin and polymer was measured using a GPC column (G2000HXL: 2, G3000HXL: 1) manufactured by Tosoh Corporation at a flow rate of 1.0 ml. Per minute, elution solvent: tetrahydrofuran, column temperature: 40 ° C., and analyzed by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard.

The performance of the antireflection film-forming composition was evaluated in the following manner.
optical properties:
After spin-coating the anti-reflective film forming composition on a silicon wafer having a diameter of 8 inches, the composition is heated on a hot plate at 345 ° C. for 120 seconds to form a 0.1 μm-thick anti-reflective film. The film was measured for refractive index (n value) and absorbance (k value) at a wavelength of 248 nm using a spectroscopic ellipsometer UV-1280E manufactured by KLA-TENCOR, and using a spectroscopic ellipsometer MOSS-ESVG DEEP UV manufactured by SOPRA. Then, the n value and the k value at a wavelength of 193 nm were measured.

Formation of positive resist pattern for KrF:
The composition for forming an anti-reflection film was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated on a hot plate at 345 ° C. for 120 seconds to form an anti-reflection film having a thickness of 0.6 μm. Thereafter, a KrF resist composition solution (trade name: KRFM20G, manufactured by JSR Corporation) was spin-coated on the antireflection film, and prebaked on a hot plate at 140 ° C. for 60 seconds to form a 0.61 μm-thick film. A resist film was formed. Thereafter, using a Nikon Corporation stepper NSR2005EX12B (wavelength: 248 nm), a KrF excimer laser is used to form a line and space pattern having a line width of 0.22 μm with a line width of 1: 1 using a KrF excimer laser through a mask pattern. Hereinafter, it is referred to as “optimum exposure time”). Then, after post-baking on a hot plate at 140 ° C. for 90 seconds, development is performed at 23 ° C. for 30 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, washed with water, and dried to form a positive resist pattern. Formed.

Formation of positive resist pattern for ArF:
An antireflection film composition was spin-coated on a silicone wafer having a diameter of 8 inches, and baked on a hot plate at 345 ° C. for 120 seconds to form an antireflection film having a thickness of 0.6 μm. Thereafter, the resist composition solution for ArF obtained in Reference Example 1 described later is spin-coated on this antireflection film, and prebaked on a hot plate at 130 ° C. for 90 seconds to form a 0.5 μm-thick resist film. Formed. Thereafter, exposure was performed for an optimum exposure time through a mask pattern using an ArF excimer laser exposure apparatus (lens numerical aperture: 0.60, exposure wavelength: 193 nm) manufactured by ISI. Thereafter, the film is post-baked on a hot plate at 130 ° C. for 90 seconds, developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, washed with water, and dried to form a positive resist. A pattern was formed.

Standing wave prevention effect:
The formation of an antireflection film and the formation, exposure, and development of a resist film were performed as described above, and the presence or absence of the effect of standing waves on the resist film was observed and evaluated using a scanning electron microscope.
Intermixing prevention effect:
An anti-reflection film was formed as described above, and the obtained anti-reflection film was immersed in propyl glycol monomethyl ether acetate at room temperature for 1 minute, and the change in film thickness before and after immersion was measured using a spectroscopic ellipsometer UV1280E (KLA-TENCOR) When the film thickness was not changed, the evaluation was “○”, and when the film thickness was changed, “X” was evaluated.

Preparation Example 1 (Preparation of ArF resist composition solution)
In a separable flask equipped with a reflux tube, under a nitrogen stream, 8-methyl-8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodec-3-ene 29 parts, 8-methyl-8-hydroxytetracyclo [4.4.0.1 ^2,5 .
[ ^17,10 ] dodeca-3-ene 10 parts, maleic anhydride 18 parts, 2,5-dimethyl-2,5-hexanediol diacrylate 4 parts, t-dodecylmercaptan 1 part, azobisisobutyronitrile 4 And 60 parts of 1,2-diethoxyethane were charged and polymerized at 70 ° C. for 6 hours with stirring. Thereafter, the reaction solution was poured into a large amount of a mixed solvent of n-hexane / i-propyl alcohol (weight ratio = 1/1) to coagulate the resin, and the coagulated resin was washed with the mixed solvent several times, and then vacuumed. After drying, the content of the structural unit represented by the following formula (a), (b) or (c) is 64 mol%, 18 mol% and 18 mol%, respectively, and Mw is 27,000. The resin was obtained with a yield of 60%.

  80 parts of the obtained resin, 1.5 parts of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate and 0.04 part of tri-n-octylamine were converted to propylene glycol monomethyl ether. The resultant was dissolved in 533 parts of acetate to prepare a resist composition solution for ArF.

Example 2 (Synthesis of polymer (III))
In a separable flask equipped with a thermometer, under a nitrogen atmosphere, 8 parts of acenaphthylene, 4 parts of 5-hydroxymethylacenaphthylene, 50 parts of n-butyl acetate and 4 parts of azobisisobutyronitrile were charged and stirred. Polymerization was carried out at 80 ° C. for 7 hours. Thereafter, the reaction solution was diluted with 100 parts of n-butyl acetate, and the organic layer was washed with a large amount of a mixed solvent of water / methanol (weight ratio = 1/2). (III) was obtained.

Example 3 (Synthesis of polymer (IV))
A separable flask equipped with a thermometer was charged with 6 parts of acenaphthylene, 5 parts of 4-hydroxymethylstyrene, 48 parts of n-butyl acetate and 4 parts of azobisisobutyronitrile under a nitrogen atmosphere, and stirred at 75 ° C. For 7 hours. Thereafter, the reaction solution was diluted with 100 parts of n-butyl acetate, and the organic layer was washed with a large amount of a mixed solvent of water / methanol (weight ratio = 1/2). (IV) was obtained.

Example 4 (Synthesis of polymer (V))
In a separable flask equipped with a thermometer, 6 parts of acenaphthylene, 5 parts of 2-hydroxymethyl-6-vinylnaphthalene, 48 parts of 2-heptanone and 4 parts of azobisisobutyronitrile were charged and stirred under a nitrogen atmosphere. The polymerization was carried out at 75 ° C. for 7 hours. Thereafter, the reaction solution was diluted with 100 parts of 2-heptanone, and the organic layer was washed with a large amount of a mixed solvent of water / methanol (weight ratio = 1/2). Polymer (V) was obtained.

Example 5 (Evaluation of antireflection film forming composition)
10 parts of the polymer (III) obtained in Example 2, 0.5 part of bis (4-t-butylphenyl) iodonium 10-camphorsulfonate and 4,4 ′-[1- {4- (1- [4- After dissolving 0.5 part of [hydroxyphenyl] -1-methylethyl) phenyl {ethylidene] bisphenol in 89 parts of ethyl lactate, the solution was filtered through a membrane filter having a pore size of 0.1 μm to obtain an antireflection film-forming composition. Prepared. Next, performance evaluation was performed on this composition. Table 1 shows the evaluation results.

Example 6 (Evaluation of antireflection film forming composition)
10 parts of the polymer (III) obtained in Example 2, 0.5 parts of bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate and 4,4 ′-[1- {4- (1- After dissolving 0.5 part of [4-hydroxyphenyl] -1-methylethyl) phenyl {ethylidene] bisphenol in 89 parts of ethyl lactate, the solution is filtered through a membrane filter having a pore size of 0.1 μm to form an antireflection film. A composition was prepared. Next, performance evaluation was performed on this composition. Table 1 shows the evaluation results.

Example 7 (Evaluation of antireflection film forming composition)
In Example 5, reflection was carried out in the same manner as in Example 5, except that 10 parts of the polymer (IV) obtained in Example 3 was used instead of 10 parts of the polymer (III) obtained in Example 2. A composition for forming a protective film was prepared. Next, performance evaluation was performed on this composition. Table 1 shows the evaluation results.

Example 8 (Evaluation of antireflection film forming composition)
In the same manner as in Example 6, except that 10 parts of the polymer (III) obtained in Example 2 was used instead of 10 parts of the polymer (III) obtained in Example 2, the reflection was performed in the same manner as in Example 6. A composition for forming a protective film was prepared. Next, performance evaluation was performed on this composition. Table 1 shows the evaluation results.

Example 9 (Evaluation of antireflection film forming composition)
In Example 6, the reflection was performed in the same manner as in Example 6, except that 10 parts of the polymer (V) obtained in Synthesis Example 1 was used instead of 10 parts of the polymer (III) obtained in Example 2. A composition for forming a protective film was prepared. Next, performance evaluation was performed on this composition. Table 1 shows the evaluation results.

Comparative Example 1
A positive resist pattern for KrF and a positive resist pattern for ArF were formed without using the antireflection film-forming composition, and the performance was evaluated. Table 1 shows the evaluation results.

Claims (8)

Acetoxymethyl acenaphthylene represented by the following formula (1).

Hydroxymethyl acenaphthylene represented by the following formula (2).

A polymer having a structural unit represented by the following formula (3) and having a polystyrene equivalent weight average molecular weight of 500 to 10,000 as measured by gel permeation chromatography.

[In the formula (3), R ¹ represents a hydrogen atom or a monovalent organic group, and R ² and R ³ independently represent a monovalent atom or a monovalent organic group. ]   A composition for forming an antireflection film, comprising the polymer according to claim 3 and a solvent. An antireflection film-forming composition comprising a polymer having a structural unit represented by the following formula (4) and a solvent.

[In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent atom or a monovalent organic group, and n is 0 or 1. ] A polymer having the structural unit represented by the formula (3) according to claim 3 and the structural unit represented by the formula (4) according to claim 5, wherein the polymer has a structure represented by the formula (3) according to claim 3. A polymer having a structural unit represented by the following formula (5) and a structural unit represented by the following formula (5) and a structural unit represented by the formula (4) and the following formula (5) A composition for forming an antireflection film, comprising at least one selected from the group of polymers having structural units and a solvent.

[In the formula (5), R ⁶ and R ⁷ independently represent a monovalent atom or a monovalent organic group. ]   The antireflection film-forming composition according to any one of claims 4 to 6, further comprising an acid generator.   The antireflection film-forming composition according to any one of claims 4 to 7, further comprising a crosslinking agent.